Terpene derivatives



S fPA'lEN'l osmos- UNITED STATE TERPENE DERIVATIVES Alfred L.Rummelsburg, Wilmington, DeL, signor to Hercules Powder Company,Wilmington, Del., a corporation o1"Delaware No Drawing. Application May31, 1941,

Serial No. 396,219

Claims. (Cl. 260-609) This invention relates to methods for theproduction of sulfur-containing terpene compounds and to the productsformed thereby; more particularly, it relates to the production ofsulfurcontaining compounds of acyclic terpenes having three double bondspermolecule and to the products formed thereby. V

In accordance with this invention, it has been found that when anacyclic terpene having three double bondsper molecule, in any of itsmonomeric or polymeric modifications, is reacted with sulfur or varioussulfur-containing compounds,

there results a series of highly interesting and useful compounds. Thereaction products themselves have important uses as fio t'ion agents. Inaddition, they serve as inter nediates for the preparation ofplasticizers for halofienated rubber, adhesives, etc.

As stated hereinabove, any-of the. monomeric or polymeric forms ofacyclic terpenes having a three double bonds per molecule, as forexample,

. include polymerization with phosphoric acid catalysts, such as,orthophosphoric acid, tetraphosphoric acid, ,hypophosphoric acid,metaphosphorlc acid, pyrophosphoric acid, etc., also with metal halidecatalysts, such as, stannic chloride,

aluminum chloride, zinc chloride, boron trifluoride and its molecularcomplexes with ethers and acids, etc. In addition, activated clays,including silica gel, fuller's earth, diatomaceous earth, activatedalumina, etc., may be employed to accomplish the polymerization. Thepolymerization may be carried out with or without the use or an inert,volatile, organic solvent, such as, .benzene, xylene, gasoline, ethylenedichloride, etc. For additional information relating to the particularprocedures employed, see co-pending applications for United StatesLetters Patent of A. L. Rummelsburg, Serial No. 370,664, filed December18.

.phoric acid catalysts, a liquid productis formed containing asubstantial quantity of the dimer. In actual practice, the product willcontain from about 7 to. 95% of thedimer, depending upon the conditionsof reaction, such as, the type of phosphoric acid used, theconcentration of catalyst, the particular solvent, the temperature ofreaction, etc. The thiocyanate value of the product may vary from about120 to about 240. If desired,'a fter the catalyst has been removed, thesubstantially pure dimer may beseparated from the remaining constituentsby distillation underreduced pressure. The substantially pure dimer isthe preferred form of polymeric acyclic terpene to be employed inaccordance with the invention.

In carrying out the polymerization with metal halide catalysts, liquidpolymers may also be obtained following .the procedure as given in my00- pending application for United States Letters Patent, Serial No.370,664, filed December 18, 1940; however, by employing particular metalhalides and suitably controlling the conditions of I the reaction, solidpolymers of the acyclic terpene employed result. For example, whena'metal' out over wide ranges of temperature and using various inertsolvents. Preferably, however, to

form solid polymers, the reaction is carried out.

at a temperature within the range 0! from about 35 C. to about C. withthe acyclic terpene dissolved in ahalogenated organic solvent, such as,ethylene dichloride, etc.

These solid polymers which are prepared by the processes above describedcontain substantial quantities of polymeric constituents higher than thedimer. It has been determined that these organic solids have at leastabout of polymeric constituents higher than the dimer. They are furthercharacterized by ha g lower thiocyanate-values than do the liquipolymers, the values for the former Ialling within the range of fromabout 20 to about 80.

In accordance with this lnventlon then, an acyclic terpene such asallo-oclmene is reacted" with sulfur or a sulfur-containing compound."

The sulfur-containing compounds which may I 'be utilized in carrying outthe reaction comprise hydrogen sulfide, sulfur halides such as- SzBrz,8201:, SaFr, 810, etc., and alkyl mercaptans such as methyl, ethyl,propyl, butyl, etc., mercaptans.

1940, and Serial No. 370,665, filed December 18, v

1940,. If the polymerization is carried out with phos- In the case ofhydrogen sulfide and the allwl mercaptans, a catalyst of the type to.be-described hereinafter will be employed. With sulfur-and the sulfurhalides, however, a catalyst is not necessary, nor is it desirable.

In. carrying out the reaction, the acyclic terpene may or may not bedissolved in an inert solvent such as benzene, toluene, butanol,gasoline, etc., as desired. It is often preferable, however, when asolid polymeric form of the acyclic terpene is employed, to carry outthe reaction with an inert solvent present in order to assure bettercontact of the reactants. Employing an acyclic terpene or its solution,the reactant is contacted with the desired sulfur or sulfur-containingreactant either with or without the presence of a suitable catalyst asdetermined by the particular reactants employed. Desirably, the reactionmixture is agitated either throughout the whole or part of the reactionperiod. The reaction may be carried out at various temperatures and overdifferent periods of time. While a temperature within the range of fromabout 0 C. to about 250 C. for a period of from about 1 hour to about100 hours is suitable for the reaction, a temperature within the rangeof from about 20 C. to about 180 C. and for a period of from about 2hours to about 24 hours, is preferably employed. Ordinarily atmosphericpressure is conveniently employed in carrying out the reaction. However,when one or more-of the reactants is gaseous at the temperature at whichthe reaction is carried out, superatmospheric pressure is preferredinasmuch as its use results in increased speed of reaction. In thisinstance, the pressure may vary from about atmospheric to about 100atmospheres. As heretofore stated, a catalyst will be employedto promotethe reaction when either hydrogen sulfide or an alkyl mercaptan'isemployed. Suitable catalysts comprise acids, such as, sulfuric acid,phosphoric acid-acetic acid, etc.; acid anhydrides, such as phosphoruspentoxide, etc.; bases, such as, potassium hydroxide,

sodium hydroxide, monoamylamine, diamylamine, triamylamine, theethanolamines, aniline, pyridine, etc.; contact catalysts, such--' as,activated carbon, silica gel, etc.; dimethyl sulfate; metallic aluminum;and metal sulfides. In addition, various combinations of catalysts maybe used in place of a single catalyst. It is preferred in carrying outthe reaction inherent in this invention to use an acid catalyst, and itis still further preferred that such a catalyst be used in conjunctionwith a contact catalyst, such as, activated charcoal, silica gel,fullers earth, activated magnesium silicate, bauxite, activated alumina,etc. If desired, certain of these contact catalysts, may, prior to usehe calcined at temperatures between about 250 C. and about 500 C.

The amount of catalyst to be employed, when required, may be varied fromabout 0.01 to about 2.00 times the amount of acyclic terpene used,however, some reaction will take place when greater or lesser employed.The mineral acid catalysts, when such are employed, will desirably beemployed in the form of their aqueous solutions having a mineral acidconcentration within the range of from about 20 to about 100%. whensulfuric acid is employed as the catalyst, however, it is preferablyemployed in the form of a solution having a concentration with respectto the suliuric acid not greater than 75%. Otherwise, sulfonation of theacyclic terpene may take place. when using mineral acids ac catalysts,it is advisable to add the catalyst at intervals amounts of the catalystare during the progress of the reaction rather'than allat once at thestart of the reaction. These.

,acid catalysts lose much of their activity after having once been usedin the reaction, but activity may be restored by adding a small amountof anhydrous or concentrated acid to the spent catalyst. Reactivationmay also be accomplished by heating the spent catalyst at a temperatureof from about C. to about 120 C. for about an hour, cooling, andfiltering through activated charcoal.

At the end of the reaction period, the reaction mixture, if an acidcatalyst has been employed in accordance with this invention, willseparate into two layers. The layer containing the acyclic terpenereaction product may be separated and the catalyst remaining in theproduct may be removed in any desirable manner, preferably by washingwith water. Any inert solvent which may have been employed in carryingout the reaction may be removed, preferably by distillation underreduced pressure. The product may then be dried in any desired manner.If other catalysts have been employed in accordance with the invention,they may be removed by methods known to the art. a

There follow several specific examples which illustrate particularembodiments of the principles underlying this invention. These examples,however, are not to be construed as being limiting. All parts andpercentages are by weight unless otherwise indicated.

Example 1 Four hundred and ten parts of -monomeric alloocimene pure) and850 parts of 85% orthophosphoric acid were reacted with hydrogen sulfideat a temperature of from 25 C. to 40 C. and at a pressure of 175 to 200lbs. per sq. in. for 14 hours in a rotating autoclave. After thisreaction period, the contents of the autoclave were removed and allowedto separate into two layers. The phase containing the treatedallo-ocimene was removed and washed with water to remove the catalyst.The product was then dried with anhydrous Na2SO4 and thereafter shakenwith several parts of Filter-Cel (diatomaceous earth). 447 parts of anamber-colored liquid remained which analyzed 16.8% sulfur.

Erample 2 To 75 parts of monomeric allo-ocimene (62 pure) were added 24parts of flowers of sulfur and the mixture heated at C. for a period of72 hours with intermittent agitation. The other constituents of thecrude allo-ocimene employed were a-pinene, dipentene and a. small amountof unidentified terpenes.; The sulfur dissolved completely withoutevolution of hydrogen sulfide. After the initial reaction period, thereaction mixture was heated at 195 C. for 4 hours. Some hydrogen sulfideevolved. The product was a dark-colored liquid having a sulfur contentof 15.0%.

Example 3 To 100 parts of monomeric allo-ocimene (60% pure) were added48 parts of ethyl mercaptan and parts of 85% orthophosphoric acid, andthe mixture was agitated at 25 C. to 30 C. for 11 hours in a rotatingautoclave. The allo-ocimene employed contained in addition to thealloocimene, a-pinene, dipentene and a small amount of unidentifiedterpenes. The resulting mixture was then allowed to stand at about 23 C.for 48 hours. The mixture was found to have separated Example 4Thirty-eight parts of sulfur monochloride were added to 75 parts ofallo-ocimene (90% pure) over a period of 0.5 hour with agitation andcooling to maintain a temperature of 12 C.-24 C. No hydrochloric acidwas evolved as a result of the reaction which took place. There was,however, a decided increase in the viscosity of the mixture. The productwas then allowed to stand at 25 C.-30 C. for 1'70 hours. It wasafterwards dissolved in ether, water washed and dried with anhydroussodium sulfate. The ether was removed by distillation to yield adark-colored viscous liquid having asulfur content of 14.9% and achlorine content of 12.3%.

Example One hundred and fifty parts of polymerized allo-ocimene,consisting substantially entirely. of

the dimer, and 35 parts of flowers of sulfur were gradually heated to atemperature of. 180 C. under an air condenser over a period of 2 hourswith agitation. Heating was continued at 180 C. to 200 C. for about 6hours. Some hydrogen sulfide was evolved. The product was a viscous oilat room temperature containing about; 15% of combined sulfur.

Example 6 sulfur.

Example 7 Two hundred parts of allo-ocimene (95% pure) 300 parts of 85%orthophosphoric 'acid and parts of activated carbon were agitated in anatmosphere of hydrogen sulfide at a pressure of 180 to 250 lbs. per sq.in. at a temperature of 25 C to 40 C. for aperiod of .24 hours. The acidphase was separated and the remaining phase containing the allo-ocimenereaction product was then water washed to remove traces of acid. Theproduct was then filtered and dried with anhydrous sodium'sulfate. Itwas found to contain 22% of combined sulfur.

When, in carrying out the reaction according to the processes of thisinvention, hydrogen sulflde is employed as the sulfur-containingreactant, the hydrogen sulfide adds to the acyclic terpene at theunsaturated double bonds with the resultant formation of mercaptansand/or sulfides. The proportion of these materials in molecule ofhydrogen sulfide and one molecule of unsaturated terpene compound,whereas by the interaction of several molecules of each reactant or bythe reaction of the mercaptans first formed with itself or withunreacted acyclic terpene, various sulfides or thio-ethers may resuit.In the presence of an oxidizing agent such as air, the mercaptans may befurther changed to dior polysulfides. 'In .addition, poly-mercaptans mayresult from the addition of hydrogen sulfide to more than one doublebond of a single acyclic terpene molecule.'

When, in carrying out the reaction according to the processes of thisinvention, a sulfur halide is employed as the sulfur-containingreactant,

. the sulfur halide adds to the acyclic terpene at the double bonds. Theaddition reaction takes place predominately when the temperature of thereaction mixture is held within the range of from 0 C. to about 30 C. Athigher temperatures, reactions other than straight addition take place.

When an alkyl mercaptan is employed .in accordance with this invention,an addition reaction takes place at the unsaturated centers of theacyclic terpene and polymerized acyclic terpene resulting in theformation of an acyclic terpene alkyl sulfide.

When elemental sulfur is employed in accordance with this invention, anaddition reaction at the double bonds of the acyclic terpene orpolymerized acyclic terpene takes place. At

, temperatures of from about 60 C. to about 7 from the group consistingof the monomers and polymers of acyclic terpenes having three double theproduct may vary depending upon the conditions of reaction.Mono-mercaptans will be.

formed by simple combination between one the liberation of hydrogensulfide to form com-- plex sulfur-containing condensates.

It will be understood that it is not the intent to limit the instantinvention to the theoretical limitations as hereinbeforedescribed butthat the invention as contemplated is directed to the products resultingfrom the application of the methods of the invention'as broadlydescribed.

The sulfur-containing compounds of acyclic terpenes produced inaccordance with this invention may be used as flotation agents. They mayin addition, he used as intermediates for the production of plasticizersfor halogenated rubber, adhesives. etc.

It will be understood that the details and examples hereinbefore setforth are illustrative only and that the invention as broadly describedand claimed is in no way limitedthereby. I

This application is a continuation-impart of my application for UnitedStates Letters Patent, Serial No. 382,749, filed March 11, 1941.

What I claim and desire to protect by Letters Patentis:

1. The reaction product of a materialselected tion of matter whichcomprises reacting a ma.-

terial selected from the group consisting of the monomers and polymersof an acyclic terpene having three double bonds per molecule, withhydrogen sulfide, in the presence of a catalyst until reaction is atleast partially complete.

7. The method of producing'a new composition of matter which comprisesreacting at a temperature within the range of from about 0 C. to about250 C., a material selected from the group consisting of the monomersand polymers of an acyclic terpene having three double bonds permolecule, with hydrogen sulfide, in the presence of a catalyst untilreactionis at least partially complete.

8. The method of producing a sulfur-contain- 9. The method of producinga sulfur-containing compound of allo-ocimene which comprises reactingmonomeric allo-ocimene with hydrogen sulfide in the presence ofphosphoric acid.

10. The method of producing a sulfur-containing compound of allo-ocimenewhich comprises reacting monomeric allo-ocimene with hydrogen sulfide inthe presence of a mixed catalyst comprising a contact catalyst and anacid catalyst.-

ALFRED L. RUMMELSBURG.

